U.S. patent number 5,130,413 [Application Number 07/574,862] was granted by the patent office on 1992-07-14 for process for producing unsaturated group-terminated high-molecular weight polyalkylene oxide.
This patent grant is currently assigned to Kanegafuchi Kagaku Kogyo Kabushiki Kaisha. Invention is credited to Yukimitsu Asai, deceased, by Keiji Asai, legal representative, by Yoshie Asai, legal representative, Hiroyuki Kawata, Tooru Nakagawa.
United States Patent |
5,130,413 |
Asai, deceased , et
al. |
July 14, 1992 |
Process for producing unsaturated group-terminated high-molecular
weight polyalkylene oxide
Abstract
A process for producing an unsaturated group-terminated
high-molecular weight polyalkylene oxide by adding an alkali metal
and/or an alkali metal compound capable of producing an alkali
metal hydroxide on reaction with water to a hydroxyl-terminated
polyalkylene oxide having a repeating unit represented by formula
--R.sup.1 --O-- (wherein R.sup.1 represents a divalent alkylene
group having from 2 to 8 carbon atoms) to substitute the hydrogen
atom of the hydroxyl end group with an alkali metal (alkoxidation)
the resulting polyalkylene oxide is reacted with a polyhalogen
compound to increase the molecular weight of the polyalkylene oxide
and then additional alkali metal and/or alkali metal compound is
added before reacting the resulting high-molecular weight
polyalkylene oxide with an unsaturated halogen compound to
introduce an unsaturated group to the molecular chain terminals.
The first addition of alkali metal and/or alkali metal compound
capable of producing an alkali metal hydroxide on reacting with
water is added in an amount equivalent to or less than the hydroxyl
end groups of said polyalkylene oxide and second addition of alkali
metal and/or alkali metal compound is added in an amount equivalent
to or greater than the remaining hydroxyl end groups.
Inventors: |
Asai, deceased; Yukimitsu (late
of Niigata, JP), Asai, legal representative; by Keiji
(Aichi, JP), Asai, legal representative; by Yoshie
(Aichi, JP), Kawata; Hiroyuki (Kobe, JP),
Nakagawa; Tooru (Takasago, JP) |
Assignee: |
Kanegafuchi Kagaku Kogyo Kabushiki
Kaisha (Osaka, JP)
|
Family
ID: |
16851706 |
Appl.
No.: |
07/574,862 |
Filed: |
August 30, 1990 |
Foreign Application Priority Data
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|
|
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Aug 31, 1989 [JP] |
|
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1-226860 |
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Current U.S.
Class: |
528/408;
525/359.3; 528/409; 568/613; 568/616; 568/617; 568/618;
568/619 |
Current CPC
Class: |
C08G
65/32 (20130101); C08G 65/337 (20130101) |
Current International
Class: |
C08G
65/00 (20060101); C08G 65/32 (20060101); C08G
65/337 (20060101); C08G 065/32 () |
Field of
Search: |
;528/408,409
;568/613,616,617,618,619 ;525/359.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
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0066179 |
|
Dec 1982 |
|
EP |
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0196569 |
|
Oct 1986 |
|
EP |
|
Other References
Patent Abstracts of Japan, vol. 3, No. 7 (C-35) (3011) Jan. 30,
1979 and JP-A-53 134 095 (Kanegafuchi Kagaku Kogyo K.K.) Nov. 22,
1979. .
Database WPIL, No. 82-86772E, Derwent Publ. Ltd., London, GB; and
JP-A-57143324/Kanegafuchi Chem. Apr. 9, 1982..
|
Primary Examiner: Foelak; Morton
Assistant Examiner: Wright; Shelley A.
Attorney, Agent or Firm: Armstrong, Nikaido, Marmelstein,
Kubovcik & Murray
Claims
What is claimed is:
1. A process for producing an unsaturated group-terminated
high-molecular weight polyalkylene oxide, comprising: (a) adding an
alkali metal, an alkali metal compound capable of producing an
alkali metal hydroxide on reaction with water, or a mixture
thereof, to hydroxyl-terminated polyalkylene oxide comprising a
repeating unit represented by formula --R.sup.1 --O--, wherein
R.sup.1 represents a divalent alkylene group having from 2 to 8
carbon atoms, to replace the hydrogen atom of the hydroxyl end
group with an alkali metal, (b) reacting the resulting polyalkylene
oxide with a polyhalogen compound to increase the molecular weight
of the polyalkylene oxide; (c) adding an alkali metal, an alkali
metal compound capable of producing an alkali metal hydroxide on
reaction with water, or a mixture thereof, to the polyalkylene
oxide of increased molecular weight, and (d) reacting the
polyalkylene oxide of increased molecular weight with an
unsaturated halogen compound to introduce an unsaturated group to
the molecular chain terminals, wherein said alkali metal, alkali
metal compound capable of producing an alkali metal hydroxide on
reaction with water, or a mixture thereof, is added before step (b)
in an amount equivalent to or less than the hydroxyl end groups of
said polyalkylene oxide and then added before step (d) in an amount
equivalent to or more than the remaining hydroxyl end groups.
2. A process as claimed in claim 1, wherein said
hydroxyl-terminated polyalkylene oxide is at least one
hydroxy-terminated polyalkylene oxide selected from the group
consisting of polyoxyethylene glycol, polyoxyethylene triol,
polyoxyethylene traol, polyoxypropylene glycol, polyoxypropylene
triol, polyoxypropylene tetraol and polyoxybutylene glycol.
3. A process as claimed in claim 1, wherein said alkali metal is at
least one alkali metal selected from the group consisting of
sodium, potassium and mixtures thereof.
4. A process as claimed in claim 1, wherein said alkali metal
compound is an alkali metal hydride.
5. A process as claimed in claim 1, wherein said alkali metal
compound is an alkali metal alkoxide.
6. A process as claimed in claim 5, wherein said alkali metal
alkoxide is an alkali metal alkoxide dissolved in an alcohol.
7. A process as claimed in claim 1, wherein said polyhalogen
compound is a dihalogen alkylene compound.
8. A process as claimed in claim 1, wherein said unsaturated
compound is an organic halogen compound represented by formula:
wherein R.sup.2 represents a divalent organic group; and X
represents a halogen atom.
9. A process as claimed in claim 1, wherein said unsaturated
halogen compound is an allyl halide.
Description
FILED OF THE INVENTION
This invention relates to a process for producing an unsaturated
group-terminated high-molecular weight polyalkylene oxide.
BACKGROUND OF THE INVENTION
A polyalkylene oxide having an unsaturated end group is useful as a
crosslinking agent or a modifier in vinyl polymerization.
The reaction between an unsaturated group-terminated polyalkylene
oxide and a hydrosilane having a hydrolyzable group produces a
polymer having a crosslinking silicon end group which is useful as
a moisture-curing polymer as disclosed in JP-A-52-73998 (the term
"JP-A" as used herein means an "unexamined published Japanese
patent application").
The polyalkylene oxides are, in most cases, required to have a high
molecular weight of from about 5,000 to 20,000. However, such a
high-molecular weight polyalkylene oxide is not readily available
on the market.
JP-A-53-134095 discloses a process for producing an unsaturated
group-terminated high-molecular weight polyalkylene oxide, in which
a hydroxyl-terminated polyalkylene oxide having a relatively low
molecular weight is used as a starting material, which comprises
converting the hydroxyl end group to an alkoxide group in the
presence of an alkali metal hydroxide (alkoxidation). Thereafter a
plurality of the polyalkylene oxide molecules are connected to one
another by using a polyhalogen compound to increase the molecular
weight of the starting polyalkylene oxide (1st step), and then the
hydroxyl end groups are converted to unsaturated groups by using an
unsaturated halogen compound. This process is illustrated by the
following reaction scheme: ##STR1##
This reference additionally discloses a process in which an alkali
metal or an alkali metal compound, capable of producing an alkali
metal hydroxide on reaction with water, such as an alkali metal
hydride and an alkali metal alkoxide, (hereinafter an alkali metal
and an alkali metal compound will be inclusively referred to as an
alkoxidizing agent) can be used in place of the alkali metal
hydroxide to alkoxidize the hydroxyl end group. Because such
alkoxidizing agents have a higher activity than an alkali metal
hydroxide, an about equivalent amount of the alkoxidizing agent can
be used to conduct the reaction so that purification of the product
is easy. However, when the reaction scheme shown above is followed
using alkoxidizing agents, the increase in molecular weight and the
ability to introduce an unsaturated bond to the product produced in
the first step are insufficient, which highligths the fact that the
reaction conditions must be strictly controlled before a desired
reaction can proceed.
SUMMARY OF THE INVENTION
An object of this invention is to provide a process for producing
an unsaturated group-terminated high-molecular weight polyalkylene
oxide by using an alkoxidizing agent which makes purification of
the product easy.
Another object of this invention is to provide a process for
producing an unsaturated group-terminated high-molecular weight
polyalkylene oxide in which the increase in molecular weight the
introduction of an unsaturated group proceeds easily and
sufficiently.
The inventors have conducted extensive investigations and have
found that the above objects are accomplished by a process which
comprises adding an alkali metal and/or an alkali metal compound
capable of producing an alkali metal hydroxide on reacting with
water to a hydroxyl-terminated polyalkylene oxide comprising a
repeating unit represented by formula --R.sup.1 --O-- (wherein
R.sup.1 represents a divalent alkylene group having from 2 to 8
carbon atoms) to substitute the hydrogen atom of the hydroxyl end
group with an alkali metal (alkoxidation), reacting the resulting
polyalkylene oxide with a polyhalogen compound to increase the
molecular weight of the polyalkylene oxide (hereinafter referred to
as a 1st step), and reacting the resulting high-molecular weight
polyalkylene oxide with an unsaturated halogen compound to
introduce an unsaturated group to the molecular chain terminals
(hereinafter referred to as a 2nd step), wherein said alkali metal
and/or alkali metal compound capable of producing an alkali metal
hydroxide on reaction with water is added before the 1st step in an
amount equivalent to or less than the number of hydroxyl end groups
of said polyalkylene oxide and then before the 2nd step additional
alkali metal and/or alkali metal compounds are added to the
reaction mixture in an amount equivalent to or greater than the
remaining hydroxyl end groups.
DETAILED DESCRIPTION OF THE INVENTION
The process of the present invention is characterized in that
alkoxidation of the hydroxyl end groups of the starting
polyalkylene oxide with an alkoxidizing agent is carried out in two
divided stages, once before the 1st step (increase of molecular
weight) and then before the 2nd step (introduction of an
unsaturated group), to different degrees.
The reason why the alkoxidation reaction realizes progresses so
easily to produce high of molecular weight products with introduced
unsaturated groups can be accounted for as follows:
In the process of JP-A-53-134095, alkoxidation is effected only
once by using a nearly equivalent amount of an alkoxidizing agent,
e.g., an alkali metal and a highly active alkali metal compound,
before the 1st step as described in the working examples. According
to this process, if water is incorporated into the reaction system
during or after the reaction progress in the 1st step, the alkoxide
group is converted back to a hydroxyl group so that the subsequent
2nd step hardly proceeds. To avoid such an occurrence, the reaction
system should be strictly controlled in an amount of the
alkoxidizing agent and completely free from moisture.
Further, if the alkoxidizing agent is used in excess in the
alkoxidation reaction before the 1st step in an attempt to
facilitate progress of the 2nd step, undesired side reactions
occur. For example, the reaction illustrated below would take place
during the 1st step, resulting in the failure to increase the
molecular weight of the starting polyalkylene oxide: ##STR2##
In the process according to the present invention, such
disadvantages are eliminated, and an increase in molecular weight
and the introduction of an unsaturated group proceed quite
easily.
The starting polyalkylene oxide to be used in the present invention
is a polymer essentially comprising a repeating unit represented by
formula --R--O-- (wherein R.sup.1 represents a divalent alkylene
group having from 2 to 8 carbon atoms) and having a hydroxyl group
at the terminal(s) thereof. Suitable polyalkylene oxides are those
wherein R.sup.1 has from 2 to 4 carbon atoms.
A part of the hydrogen atoms of the alkylene group R.sup.1 may be
substituted with other atom or atomic group. The polyalkylene oxide
may be comprised of only the above-described repeating unit
(--R.sup.1 --O--) or may further contain other repeating units. In
the latter case, the proportion of the repeating unit of formula
--R.sup.1 --O-- is at least 50% by weight, and preferably at least
80% by weight. The polyalkylene oxide may be either linear or
branched. Linear polyalkylene oxides are frequently used.
The starting polyalkylene oxide should be terminated by a hydroxyl
group, but all the end groups may not be hydroxyl groups, and part
of them may be other groups, e.g., a methoxy group and an allyloxy
group. A necessary minimum number of hydroxyl groups per polymer
molecule is 1.1, preferably 1.5, in average.
The starting polyalkylene oxide mostly has a degree of
polymerization of about 100.
Specific examples of suitable starting polyalkylene oxides include
polyoxyalkylene polyols, e.g., polyoxyethylene glycol,
polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene
glycol, polyoxypropylene triol, polyoxypropylene tetraol,
polyoxybutylene glycol, polyoxytetramethylene glycol,
polyoxypentane glycol, polyoxyhexane glycol, polyoxyheptane glycol,
and polyoxyoctane glycol. These polymers may be used either
individually or in combinations of two or more.
The alkoxidizing agent which can be used to convert the hydroxyl
end groups of the polyalkylene oxides to alkoxide groups include
alkali metals, e.g., Na and K; and alkali metal compounds capable
of producing an alkali metal hydroxide on reaction with water. Such
alkali metal compounds include alkali metal hydrides, e.g., NaH and
KH, and alkalr metal alkoxides, e.g., CH.sub.3 ONa, CH.sub.3 OK,
C.sub.2 H.sub.5 ONa, and C.sub.2 H.sub.5 OK. The preferred compound
is an alkali metal alkoxide because it can be used in the form of a
solution and evolves no combustible gas such as hydrogen. Solvents
which can be used for dissolving alkali metal alkoxides include
alcohols, e.g., methanol and ethanol.
In the first alkoxidation reaction which is conducted before the
1st step, the alkoxidizing agent is used in an amount equivalent to
or less than the hydroxyl groups in the starting polyalkylene
oxide, preferably of from 80 to 100% eq. When the reaction system
contains water and the like, the alkoxidizing agent is also
consumed by reaction with water. This being the case, the
alkoxidizing agent should be added in an increased amount
accordingly.
What is important is that the alkoxidizing agent should not be
present in excess in the reaction system before the 1st step. As a
matter of course, only a slight excess of the alkoxidizing agent
may remain in the reaction system to be subjected to the 1st step
as long as the objects of the present invention are fulfilled.
Reaction conditions of alkoxidation are not particularly limited,
and conventional conditions of temperature and pressure can be
used. When an alkali metal alkoxide is used as, the alkoxidizing
agent, the reaction is preferably carried out at a high temperature
of 50.degree. C. or more, preferably between 100.degree. C. and
200.degree. C., under reduced pressure of not more than 50 mmHg,
preferably not more than 10 mmHg, in order to drive alcohol, a
by-product of the reaction, out of the system.
Specific examples of suitable polyhalogen compounds which can be
used in the 1st step (to increase the molecular weight of the
starting polyalkylene oxides) are methylene chloride, chloroform,
carbon tetrachloride, methylene bromide,
methyleneiodide,monochloromonobromomethane,1,1-dichloro-2,2-dimethylpropan
e, benzal chloride, benzal bromide, bis(chloromethyl)benzene,
bis(bromomethyl)benzene, tris(chloromethyl)benzene,
4,4'-bis(chloromethyl)biphenyl, and bis(chloromethyl)naphthalene.
These polyhalogen compounds may be used either individually or in
combinations of two or more. Preferred polyhalogen are dihalogen
alkylene compounds, e.g., methylene chloride and methylene
bromide.
The reaction of the 1st step can be carried out at a temperature of
from 0.degree. to 200.degree. C. under normal or reduced pressure
without any particularly limits on reaction conditions. Through the
1st step, the relatively low molecular weight of the starting
polyalkylene oxide (about 500 to 5,000) is increased to about 1,000
to 20,000.
In the second alkoxidation reaction which is conducted before the
2nd step, the amount of the alkoxidizing agent to be added is at
least equivalent to the hydroxyl end groups of the high-molecular
weight polyalkylene oxide obtained in the 1st step. However, too
large an excess results in an increase of by-products in the
following steps, which will complicate purification. In general,
the alkoxidizing agent is preferably added in such an amount that
the alkoxidizing agent may be present in the reaction system after
completion of alkoxidation of the hydroxyl end groups in 5 to 50 %
eq. excess to the alkoxide end groups.
The unsaturated halogen compound which can be used in the 2nd step
preferably includes organic halogen compounds having a vinyl group,
a highly reactive unsaturated group, and represented by the formula
CH.sub.2 .dbd.CH--R.sup.2 --X (wherein R.sup.2 represents a
divalent organic group; and X represents a halogen atom). Specific
examples of such an unsaturated halogen compound are allyl
chloride, allyl bromide, vinyl(chloromethyl)benzene,
allyl(chloromethyl)benzene, allyl(bromomethyl)benzene, allyl
chloromethyl ether, allyl(chloromethoxy)benzene, 1-butenyl
chloromethyl ether, 1-hexenyl(chloromethoxy)benzene, and
allyloxy(chloromethyl)benzene. These unsaturated halogen compounds
may be used either individually or in combinations of two or
more.
The reaction of the 2nd step can be carried out under the same
conditions as in the 1st step without any particular limits on
reaction conditions.
Upon completion of the 2nd step, there is obtained an unsaturated
group-terminated high-molecular weight polyalkylene oxide.
Thereafter, the product can be isolated through conventional
purification procedures.
By the process of the present invention, there can be easily
produced an unsaturated group-terminated high-molecular weight
polyalkylene oxide having a molecular weight of, e.g., from about
5,000 to 20,000 and containing unsaturated end groups in an amount
of, e.g., 90 mol % or more.
The present invention is now illustrated in greater detail with
reference to the following Examples, but it should be understood
that the present invention is not construed as being limited
thereto. All the percents are by weight unless otherwise
indicated.
EXAMPLE 1
In a 1 l-volume pressure vessel equipped with a stirrer in which
the atmosphere had been displaced with nitrogen was charged 320 g
(0.10 mol) of polyoxypropylene glycol having an average molecular
weight of 3,200 and containing hydroxyl end groups in a proportion
of 89% based on the total end groups (the remaining end groups were
unsaturated groups, e.g., an isopropenyl group). Subsequently, 30.9
g of a 28% solution of sodium methoxide in methanol (sodium
methoxide content: 8.66 g, 0.16 mol) was added thereto (lst
alkoxidation). The temperature was raised to 130.degree. C., and
the vessel was evacuated for 2 hours. When the inner pressure was
reduced to 1 mmHg, 5.1 g (0.06 mol) of dichloromethane was added
thereto to conduct a reaction at 130.degree. C. for 4 hours (lst
step).
The reaction system having been subjected to the first alkoxidation
before the 1st step reaction was analyzed by infrared
spectrophotometry to determine the intensity of the absorption
spectrum assigned to a hydroxyl group which appears in the vicinity
of 3500 cm.sup.-1. It was proved, as a result, that 90% of the
hydroxyl groups contained in the starting polyoxypropylene glycol
had been converted to methoxide groups.
Then, 10.3 g of a 28% solution of 2.89 g (0.054 mol) of sodium
methoxide in methanol was added to the reaction system, and the
vessel was evacuated at 130.degree. C. for 1 hour (second
alkoxidation). When the inner pressure was reduced to 1 mmHg, 8.0 g
(0.105 mol) of allyl chloride was added thereto to conduct a
reaction at 130.degree. C. for 2 hours (2nd step). The reaction
system after the second alkoxidation before the 2nd step was found
to contain 0.03 mol of sodium methoxide.
After completion of the 2nd step reaction, the reaction product was
diluted with 1000 g of n-hexane, and 50 g of aluminum silicate was
added to the solution. The mixture was stirred for 1 hour and
filtered. The filtrate was evaporated to remove the volatile
content to obtain 300 g of a polypropylene oxide polymer having an
average molecular weight of 8000. The end groups of the resulting
polymer were found to comprise 98% of an unsaturated group and 2%
of a hydroxyl group.
EXAMPLES 2 TO 5
An unsaturated group-terminated high-molecular weight polyalkylene
oxide was produced in the same manner as in Example 1, except that
various alkoxidizing agents, polyhalogen compounds and unsaturated
halogen compounds were used, and the reactions were conducted under
various conditions as shown in Table 1. The results obtained are
shown in the Table 1.
TABLE 1
__________________________________________________________________________
Example 1 Example 2 Example 3 Example 4 Example
__________________________________________________________________________
5 1st Alkoxidation: Alkoxidizing agent 28% CH.sub.3 ONa 28%
CH.sub.3 ONa 20% CH.sub.3 OK 24% CH.sub.3 ONa 20% 3OK (g) 30.9 30.9
56.2 36.0 56.2 (mol) 0.160 0.160 0.160 0.160 0.160 Reaction Temp.
(.degree.C.) 130 150 100 130 130 Reduced Pressure (mmHg) 1 1 5 3 2
Reaction Time (hr) 2 1 2 1 2 Rate of Alkoxidation (%) 90 90 90 90
90 Mol. Wt. Increase: Polyhalogen Compound CH.sub.2 Cl.sub.2
CH.sub.2 BrCl CH.sub.2 Cl.sub.2 ClCH.sub.2 OCH.sub.2 CH.sub.2
Br.sub.2 (g) 5.1 7.8 5.1 8.7 11.2 (mol) 0.060 0.060 0.060 0.077
0.063 Reaction Temp. (.degree.C.) 130 80 120 100 70 Reaction Time
(hr) 4 3 3 5 4 2nd Alkoxidation: Alkoxidizing Agent 28% CH.sub.3
ONa 28% CH.sub.3 ONa 20% CH.sub.3 OK 24% CH.sub.3 ONa 20% CH.sub.3
OK (g) 10.3 13.5 18.7 12.0 12.5 (mol) 0.054 0.070 0.053 0.053 0.036
Reaction Temp. (.degree.C.) 130 150 120 130 110 Reduced Pressure
(mmHg) 1 2 5 5 3 Reaction Time (hr) 1 2 1 1 1 Excess of Metal 0.03
0.05 0.03 0.03 0.015 Alkoxide (mol) Introduction of Unsaturated
Group: Unsaturated Halogen CH.sub.2CHCH.sub.2 Cl CH.sub.2CHCH.sub.2
Br CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 Cl CH.sub.2CHCH.sub.2
Compound ##STR3## OCH.sub.2 Cl (g) 8.0 12.2 26.3 10.1 13.9 (mol)
0.105 0.101 0.144 0.131 0.131 Reaction Temp. (.degree.C.) 130 100
120 130 100 Reaction Time (hr) 2 2 2 3 3 Produced Polyoxypropylene
Glycol: Average Molecular Weight 8000 7900 8100 9500 9000 Olefin
End Group (%) 98 98 97 98 98 OH group (%) 2 2 3 2 2 Starting
Polyoxypropylene Glycol: Average Molecular Weight 3200 3200 3200
3200 3200 OH Group (%) 89 89 89 89 89 (equivalent) 0.178 0.178
0.178 0.178 0.178 Amount Used (g) 320 320 320 320 320 (mol) 0.1 0.1
0.1 0.1 0.1
__________________________________________________________________________
EXAMPLES 6 TO 9
An unsaturated group-terminated high-molecular weight polyalkylenc
oxide was produced in the same manner as in Example 1, except that
the starting polyoxypropylene glycol was replaced with each of the
polyoxyalkylene polymers shown in Table 2 below and the reactions
were conducted under the conditions shown in the Table.
TABLE 2
__________________________________________________________________________
Example 6 Example 7 Example 8 Example 9
__________________________________________________________________________
1st Alkoxidation: Alkoxidizing Agent 28% CH.sub.3 ONa 28% CH.sub.3
ONa 28% CH.sub.3 ONa 28% CH.sub.3 ONa (g) 102.1 74.2 31.3 62.5
(mol) 0.529 0.385 0.162 0.324 Reaction Temp. (.degree.C.) 130 130
130 130 Reduced Pressure (mmHg) 1 1 1 1 Reaction Time (hr) 2 2 2 2
Rate of Alkoxidation (%) 90 90 90 90 Mol. Wt. Increase: Polyhalogen
Compound CH.sub.2 Cl.sub.2 CH.sub.2 Cl.sub.2 CH.sub.2 Cl.sub.2
CH.sub.2 Cl.sub.2 (g) 21.7 5.6 5.1 13.7 (mol) 0.255 0.066 0.06
0.161 Reaction Temp. (.degree.C.) 130 130 130 130 Reaction Time
(hr) 4 4 4 4 2nd Alkoxidation: Alkoxidizing Agent 28% CH.sub.3 ONa
28% CH.sub.3 ONa 28% CH.sub.3 ONa 28% CH.sub.3 ONa (g) 22.7 16.5
7.0 13.9 (mol) 0.118 0.086 0.036 0.072 Reaction Temp. (.degree. C.)
130 130 130 130 Reduced Pressure (mmHg) 1 1 1 1 Reaction Time (hr)
1 1 1 1 Excess of Metal 0.05 0.04 0.01 0.03 Alkoxide (mol)
Introduction of Unsaturated Group: Unsaturated Halogen CH.sub.2
.dbd.CHCH.sub.2 Cl CH.sub.2 .dbd.CHCH.sub.2 Cl CH.sub.2
.dbd.CHCH.sub.2 Cl CH.sub.2 .dbd.CHCH.sub.2 Cl Compound (g) 10.8
10.8 10.8 10.8 (mol) 0.141 0.141 0.141 0.141 Reaction Temp.
(.degree.C.) 130 130 130 130 Reaction Time (hr) 2 2 2 2 Produced
Polyalkylene Oxide: Average Molecular Weight 8000 9000 8300 11500
Olefin End Group (%) 96 98 97 98 OH Group (%) 4 2 3 2 Starting
Polyalkylene Oxide: Kind polyoxy- polyoxy- polyoxy- polyoxy-
ethylene propylene tetramethyl- hexane glycol triol lene glycol
glycol Average Molecular Weight 1200 2800 3500 2200 OH Group (%) 98
95 90 90 (mol) 0.588 0.428 0.18 0.36 Amount Used (g) 360 420 350
440 (mol) 0.3 0.15 0.1 0.2
__________________________________________________________________________
COMPARATIVE EXAMPLE
An unsaturated group-terminated high-molecular weight
polyoxyalkylene was produced in the same manner as in Example 1,
except that alkoxidation was carried out only once prior to
completion of the 1st step (molecular weight increased by using
sodium methoxide in an amount equivalent to a hydroxyl group of the
starting polyoxypropylene glycol, followed by the molecular weight
increase reaction and then the reaction for introducing of the
unsaturated end group. The resulting polymer had a low content of
an unsaturated end group.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *